A complete description of vector Bessel (vortex) beams in the context of the generalized Lorenz–Mie theory (GLMT) for the electromagnetic (EM) resonance scattering by a dielectric sphere is presented, using the method of separation of variables and the subtraction of a non-resonant background (corresponding to a perfectly conducting sphere of the same size) from the standard Mie scattering coefficients. Unlike the conventional results of standard optical radiation, the resonance scattering of a dielectric sphere in air in the field of EM Bessel beams is examined and demonstrated with particular emphasis on the EM field’s polarization and beam order (or topological charge). Linear, circular, radial, azimuthal polarizations as well as unpolarized Bessel vortex beams are considered. The conditions required for the resonance scattering are analyzed, stemming from the vectorial description of the EM field using the angular spectrum decomposition, the derivation of the beam-shape coefficients (BSCs) using the integral localized approximation (ILA) and Neumann–Graf’s addition theorem, and the determination of the scattering coefficients of the sphere using Debye series. In contrast with the standard scattering theory, the resonance method presented here allows the quantitative description of the scattering using Debye series by separating diffraction effects from the external and internal reflections from the sphere. Furthermore, the analysis is extended to include rainbow formation in Bessel beams and the derivation of a generalized formula for the deviation angle of high-order rainbows. Potential applications for this analysis include Bessel beam-based laser imaging spectroscopy, atom cooling and quantum optics, electromagnetic instrumentation and profilometry, optical tweezers and tractor beams, to name a few emerging areas of research.